Mahic Tricks Prank

Chapter
Chemical Kinetics and Nuclear Chemistry

Solutions
SECTION - A
School/Board Exam. Type Questions
Very Short Answer Type Questions :
1.
Z has zero order. What is the rate equation?

The reaction, X + Y
Sol. Rate =
2.
dx
= k[X]0 [Y]0 = k
dt
What is the rate-determining step of a reaction?
Sol. The slowest step is the rate determining step.

3.
State any one condition under which a bimolecular reaction may be kinetically of first order.
Sol. A bimolecular reaction may become kinetically of first order if one of the reactants is present in excess.
4.
Radioactive disintegration is which type of reaction?
Sol. The rate of disintegration of a radioactive substance is directly proportional to the amount of the substance
present. Hence, it is a reaction of first order.
5.
Define specific reaction rate.
Sol. Specific reaction rate is the rate of reaction when the molar concentration of each of the reactants is unity.
6.
How does the value of rate constant vary with concentration of reactant?
Sol. For a particular reaction at a particular temperature, rate constant is constant and does not depend upon the
concentrations of the reactants.
7.
Burning of carbon is highly exothermic process, yet it does not start on its own. Explain.
Sol. Energy is required to cross the energy barrier.

8.
The rate of reaction in the remaining mixture is not affected when a portion is removed for analysis.
Sol. Because rate of reaction is affected by change in concentration not amount.

9.
Which is greater in magnitude threshold energy or activation energy?
Sol. Threshold energy.

10. Whether the value of activation energy is higher in exothermic reactions or endothermic reactions and why?
Sol. Cannot be predicted without mentioning the nature of reaction.
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38
Solution of Assignment (Set-1)
Short Answer Type Questions :

11. For a reaction, the rate law is : Rate = [A] [B]1/2. Can this reaction be an elementary reaction?
Sol. For an elementary reaction, order of reaction should be equal to molecularity and further molecularity should
3
. Since, molecularity cannot be fractional, therefore,
2
for the given reaction, order is not equal to molecularity. Hence, given reaction cannot be an elementary
reaction.
be integral. For the given reaction, order of reaction =
12. For H2 (g) Br2 (g) 2HBr (g); rate
k [H2 ][Br2 ]3/2

.
[HBr]
What is the order of reaction? Write down unit of rate constant.
3
3
Sol. Order = 1 1
2
2
3
L 2
L1/ 2 mol1/ 2 s1
Hence, unit of k
mol s1
13. For the reaction,
H+
C12H22O11 + H2O
C6H 12O6 + C6H12 O6 , write
(i)
Rate of reaction
(ii)
Rate law equation
(iii) Molecularity
(iv)
Sol. (i)
Order of reaction
Rate of reaction =
d[C6H12O6 (glucose)]
d[C12H22O11 ]
= +
dt
dt
= +
(ii)
d[C6H12O6 (fructose)]
dt
It is pseudo first order reaction :
Rate = k[C12H22O11]
(iii) Molecularity is 2.
(iv)
Order is 1.
Product, if the concentration of reactant A is increased four times, rate of reaction

14. For the reaction, 3A
is doubled. Determine the order of reaction.
Sol. Rate = k[A]m
...(i)
Where m is the order of reaction.

Given,
2 rate = k[4A]m
...(ii)
From equations (i) & (ii)

m
1 1

2 4
m=
1
2
39
2NO2 is given as rate = k[NO2]2 [O2] . How will

15. The rate law of a chemical reaction, 2NO + O2
the rate of reaction change if the volume of reaction vessel is reduced to
1
th of its original value?
4
Sol. Rate = k[NO]2[O2]

Suppose a mole NO and b mole O2 are present initially in a vessel of V litre.
2
a b
r1 k
V V
V
, then for same mole of NO and O2.
4
If volume of vessel is reduced to
a
r2 k
V
b
a b
V 64k V V

4
r2 = 64 r1
i.e., rate will increase by 64 times.
16. Why the rate of a chemical reaction does not remain uniform throughout the reaction? Is it possible to have
reaction with a uniform rate?
Sol. It is because rate of reaction depends on concentration which changes with passing of time.
A reaction of zero order proceeds at a uniform rate.
17. For a reaction, the energy of activation is zero. What is the value of rate constant at 300 K, if k = 1.6 106 s1
at 280 K (R = 8.31 J K1 mol1)?
Sol. log
Ea T2 T1
k2
0
k1 2.303R T1 T2
k2
=1
k1
k2 = k1 = 1.6 106 s1
18. A first order reaction has rate constant of 102 s1. Calculate the half life period of this reaction.
Sol. For a first order reaction, t1/2 =
0.693
k
k = 102 s1
t1/2 =
0.693
10 2
= 69.3 s
19. The t1/2 of a first order reaction is 60 minutes. What percentage will be left after 240 minutes?
Sol. k =
[A ]
2.303
log 0
t
[A t ]
0.693 2.303
100
=
log
60
240
[A t ]
At = 6.25 %
40
20. The rate constant for a first order reaction involving compound A was found to be 0.082 min1. When the initial
concentration of A is 0.15 mol/L, how long will it take for the concentration of A to drop to 0.03 mole/L.
Sol. k = 0.082 min1
k
2.303
a
log
t
ax
t=
2.303
0.15
2.303
log
log 5
=
0.082
0.03
0.082
2.303
0.694
0.082
= 19.6 min.
21. The dependence of rate constant on temperature for two reactions is shown in the diagram.
ln k
1
2
1
Which reaction has the higher activation energy?

Sol. The temperature dependence of rate constant is expressed by Arrhenius equation as
ln k ln A
Slope =
Ea
RT
Ea
R
Since reaction 2 has greater negative slope, it has higher activation energy.
22. If rate of a reaction gets doubled as temperature is increased from 27C to 37C, what is the activation energy
of the reaction?
Sol. Arrhenius equation of two different temperatures is given as
log
Ea T2 T1
k2
k1 2.303R T1 T2
log2
Ea
10
2.303 8.31 300 310
Ea = 53.6 kJ
23. What happens exactly at molecular level that leads to increase in rate of reaction as temperature is raised?
Sol. According to collision theory, reaction may take place only when the molecules collide with a kinetic energy
at least equal to activation energy, otherwise, they simply bounce back. As temperature is increased, average
kinetic energy increases and fraction of colliding molecules having energy greater than activation energy
increases.
41
24. What is known as activation energy? How is the activation energy affected by
(i)
The use of a catalyst and
(ii)
A rise in temperature.
Sol. Activation energy is the extra energy which must be supplied to the reactants so that they can change into
products.
(i)
Catalyst lowers the activation energy.
(ii)
There is almost no effect on activation energy with rise in temperature.
2NOCl is doubled when concentration of Cl2 is doubled and it

25. The rate of reaction, 2NO + Cl2
becomes eight times when concentration of both NO and Cl2 are doubled. Deduce the order of reaction.
Sol. The order is 1 w.r.t. Cl2 because rate of reaction becomes double when concentration of Cl2 is doubled. When
concentration of both NO and Cl2 is double, rate becomes eight times. It means that it becomes double due
to [Cl2] and 4 times due to [NO].
Order w.r.t. NO is 2
The overall order of reaction is 2 + 1 = 3.

26. Calculate the rate of reaction from the following rate law :
d[A]
= k[A]1 [B]2
dt
When the concentrations of A and B are 0.01 M and 0.02 M respectively and k = 5.1 103 L2 mol2 s1.
Sol.
d[A]
k[A]1 [B]2
dt
Substituting the values of k, [A] and [B], we get

Rate of reaction = 5.1 103 (0.01) (0.02)2
= 5.1 103 102 4 104
= 20.4 109
= 2.04 108 mol L1 s1
27.
CO2 (g) + NO(g), the experimentally determined rate expression below 400 K is
NO2 (g) + CO(g)
Rate = k[NO2]2
What mechanism can be suggested for above reaction?
Sol. As the rate is dependent on [NO2]2, there are two [NO] terms in the slow step of the reaction.
NO2 (g) NO2 (g) NO(g) NO3 (g) Slow

NO3 (g) CO(g) CO2 (g) NO2 (g) Fast
Rate = k[NO2]2
28. What is meant by rate of reaction? Write the differential rate expressions for the following chemical reactions:
4NO(g) + 6H2O(g)
4NH3 (g) + 5O2 (g)
Sol. Relative rates of reaction are defined as change in concentration of reactant or product per unit time w.r.t. each
reactant or product.
1 d[NH3 ]
1 d[O 2 ]
1 d[NO]
1 d[H2 O]
4 dt
5 dt
4 dt
6 dt
42
29. Differentiate between reaction rate and reaction rate constant.

Sol. Points of difference between the two are given below :
Reaction rate
Reaction rate constant
1.
It is defined as change in concentration of

reactant per unit time.
1.
It is equal to rate of reaction when

concentration of reactant is unity.
2.
Its unit is mol L1 s1.
2.
Its unit depends on order of reaction.
30. The rate constant for a first order reaction is 0.0005 min1. Calculate its half life.
Sol. t1/2 =
0.693
k
t1/2 =
0.693
0.0005
t1/2 =
693 10000
1000
5
6930
5
= 1386 min
Long Answer Type Questions :
31. (a)
D + E is found to be first order in A, second order in B and zero

The reaction, 2A + B + C
order in C.
(i)
Give the differential rate law for above reaction.
(ii) What is the effect on the rate when concentration of A, B and C, each is increased two times?
(b)
Sol. (a)
Identify the reaction order, if the unit of rate constant is s1.

(i)
Rate law for above reaction is given by

r=
dx
= k[A][B]2 [C]0
dt
(ii) On increasing the concentration of A, B and C, 2 times, then

r=
dx
= k[2A] [2B]2 [2C]0
dt
= 2 4k[A] [B]2
r = 8k[A] [B]2
i.e., the rate increases 8 times.
(b)
32. (a)
(b)
Order or reaction is one.
Product.
Write rate expression for the reaction, A
A 2 the rate of reaction becomes three times when the concentration of A
For a reaction, 2A
is increased 27 times. What is the order of reaction?
(c)
For a particular reaction, the rate of reaction does not change with time. What conclusion can you draw
from this observation?
Sol. (a)
43
Rate = k[A]n (If order of reaction is n)
1
3
(b)
Order =
(c)
Zero order reaction.
33. (a)
Can activation energy of a reaction be zero?
(b)
Can a catalyst changes the Ea of a reaction? Explain.
(c)
Predict the value of rate constant (K) if temperature approaches infinite. Is the value physically reasonable?
Sol. (a)
In the Arrhenius equation rate constant, k = A e Ea /RT , where Ea is the activation energy. R is gas
constant, T is temperature on kelvin scale and A is the frequency factor. When Ea is zero then every
collision between the reactant molecules lead to the formation of product. This is not possible. Therefore,
activation energy Ea, cannot be equal to zero.
(b)
Sometimes, the catalyst may appear in the rate law expression. This is due to the reason that the
catalyst may be reactant in the slow step and may be released in the subsequent steps. For example,
for the acidic hydrolysis of methyl acetate,
CH3COOCH3
H
H2O
CH3 COOH CH3 OH
The rate law expression is, Rate = k[CH3COOCH3] [H+].

(c)
k A e Ea /RT
If T then k = A
Which is not reasonable.
34. (a)
Express the relationship between the rate of production of iodine and hydrogen in the reaction
H2 + I2
2HI
(b)
What is the rate and order of a reaction if the mechanism is
N2 + H2O2 (Slow)
2NO + H2
2H2O (Fast)
H2O2 + H2
(c)
Sol. (a)
(b)
How does rate constant is related to concentration of the reactants?
d[I2 ]
d[H2 ]
=+
dt
dt
Rate of the reaction would be determined by the slower step.

r = k[NO]2[H2]
Order of reaction = 3
(c)
35. (a)
Rate constant does not depend upon the concentration of reactants.
2NO + O2 has an activation energy of 110 kJ mol1. At 400C, the rate

The reaction, 2NO2
constant is 7.8 mol1 L s1. What is the value of rate constant at 430C?
(b)
The activation energy for the decomposition of hydrogen iodide at 581 K is 209 kJ mol1. Calculate the
fraction of molecules having energy equal to or greater than activation energy.
44
Sol. (a)
We know,
log
Ea T2 T1
k2
k1 2.303R T1 T2
log
k2
110000 703 673
7.8 2.303 8.314 673 703
log
k2
= 0.3643
7.8
k2
= 2.31
7.8
k2 = 2.31 7.8
= 18.0 mol1 L s1
(b)
Fraction of the molecules having energy equal to or greater than activation energy.
k
e Ea /RT
A
log
Ea
k
= 2.303RT
A
209500
2.303 8.314 581
= 18.8323
k
1.471 10 19
A
36. The rate law for the reaction,
2Cl2 + O2
2Cl2O
at 200C is found to be : Rate = k[Cl2O]2
(a)
How would the rate change if [Cl2O] is reduced to one third of its original value?
(b)
How many times the [Cl2O] be changed in order to double the rate?
Sol. (a)
r = k[Cl2O]2
Let the new rate = r, so
2
1
1
Cl O
r k 2 k[Cl2O]2 r
9
9
3
(b)
In order to have the rate = 2r, let the concentration of Cl2O be x.

So, 2r = kx2
...(i)
2
We know that, r = k[Cl2O]
...(ii)
Dividing equation (i) & (ii)

2r
kx 2
=
r
k[Cl2O]2
2=
x2
[Cl2O]2
x2 = 2[Cl2O]2
x = 2 [Cl2O]
hence
2 times
45
37. A first order reaction is 20% complete in 10 minutes. Calculate the time taken for the reaction to go to 80%
completion.
Sol. Applying first order equation
2.303 100
log
t
100 20
k=
2.303
100
log
= 0.0223 min1
10
80
Again applying first order equation for 80% completion
2.303 100
log
k
100 80
t=
2.303
100
log
0.0223
20
t = 72.18 min
Product, is given as a function of different initial concentrations of

38. Rate of a reaction, A + B
A and B.
1
[A] (mol L )
[B] (mol L )
Initial rate (mol L min )
0.01
0.01
0.005
0.02
0.01
0.010
0.01
0.02
0.005
Determine the order of the reaction with respect to A and with respect to B.
Sol. Let the rate of reaction be
Rate = k[A]x [B]y
From the data given, it is clear that by doubling the concentration of A, the rate also becomes double when
B is kept constant. Thus, the rate is directly proportional to concentration of A.
Rate [A], i.e., x = 1
Or the order of reaction w.r.t. A is 1.
When the concentration of A is kept constant and the concentration of B is doubled, the rate does not change,
i.e., y = 0 or the order of reaction w.r.t. B is zero.
Thus, reaction rate,
dx
k[A]
dt
2C + 3D, the rate of change in concentration of C is 1.0 mol L1 s1.

39. For the reaction, 2A + B
Calculate the rate of reaction and rates of change in concentration of A, B, C and D.
Sol. Rate of reaction =
Given,
1 d[A ]
d[B]
1 d[C]
1 d[D]
=
=
=
2 dt
dt
2 dt
3 dt
d[C]
0.1 mol L1 s 1
dt
Rate of reaction =
1 d[C]
1
= 1.0 = 0.5 mol L1 s1

2
dt
2
46
d[A] d[C]
d[A]
1.0 mol L1 s 1
1.0 mol L1 s1
dt
dt
dt
d[B]
d[B] 1 d[C]
1
0.5 mol L1 s1
=
= 1.0 = 0.5 mol L1 s1
dt
dt
2 dt
2
d[D] 3 d[C]
3
=
= 1.0 = 1.5 mol L1 s1
dt
2 dt
2
+
Acid + Alcohol, is
40. The rate law for the following reaction : Ester + H
dx
= k [ester][H3 O+ ]0 .
dt
What would be the effect on rate if :

(a)
Concentration of ester is doubled?
(b)
Concentration of H+ ion is doubled?
Sol. As given the rate law for the reaction

(a)
r1 = k[ester]1 [H3O+]0
r1 = k[a]1 [b]0
Where a and b are initial concentrations of ester and H3O+.
If concentration of ester is doubled i.e., [Ester] = 2a, by keeping [H3O+] constant, then suppose rate
becomes r2
r2 = k[2a]1 [b]0
r1 1
=
r2 2 or r2 = 2r1
(b)
r1 = k[a]1 [b] 0
If concentration of H3O+ (i.e., b) is doubled, i.e., [H3O+] = 2b, by keeping [ester] = a then suppose rate
becomes r3,
r3 = [a]1 [2b]0
r1
= 1 or r = r
1
3
r3
41. For the reaction, 2A + B +
Product,
excess
(i)
What is rate law for the reaction?
(ii)
What are units of rate and rate constant of reaction?
(iii) On increasing the concentration of A two times, of B three times and of C four times, what is the effect
on the rate of reaction?
Sol. (i)
Rate = k[A]x [B]y [C]z

Since, C is in excess, thus z = 0 and x = 2, y = 1
Rate = [A]2 [B]1 [C]0
Order = 2 + 1 + 0 = 3
(ii)
Unit of rate of reaction = mol L1 time1

Since, the reaction is of third order.
Unit of rate constant = mol2 L2 time1
47
(iii) r = k[A]2 [B]1 [C]0

r1 = k[2A]2 [3B]1 [4C]0
r1 = 12 r
Therefore, rate of reaction will increase by 12 times.
42. In a first order reaction time taken for initial concentration of a substance to become half, is 100 seconds,
then
(a)
Calculate the rate constant of reaction.
(b)
Calculate the time required to reduce the concentration of reaction to 0.0125 M from 0.05 M.
Sol. (a)
(b)
For a first order reaction,
0.693 0.693
6.93 10 3 s 1
t1/2
100
2.303
a
log
t
ax
2.303
6.93 10
log
0.05
0.0125
t = 2000 s
43. In a reaction with initially 0.12 M, the concentration of reactant is reduced to 0.06 M in 10 hour and to
0.03 M in 20 hour.
(i)
What is the order of reaction?
(ii)
What is the rate constant?
Sol. Applying first order kinetics,

k
2.303
a
log
t
ax
For case I :
2.303
0.12
0.069 hr 1
log
10
0.06
For case II :
2.303
0.12
0.069 hr 1
log
20
0.03
Reaction is of 1st order and rate constant k = 0.069 hr1.
44. Write the rate law expression and find the rate constant for
1
[A]0
[B]0
Initial rate (mol L s )
0.1
0.2
0.05
0.2
0.2
0.10
0.1
0.1
0.05
Sol. Let the rate law for the reaction is

Rate = k[A]m [B]n
0.05 = k[0.1]m [0.2]n
...(i)
0.10 = k[0.2]m [0.2]n
...(ii)
48
0.05 = k[0.1]m [0.1]n
...(iii)
Solving these equations,

m = 1, n = 0
Thus, rate = k[A]1 [B]0
Putting the values given
0.05 = k[0.1]1
k = 0.5 s1
45. Four experiments were conducted to discover how the initial rate of consumption of BrO3 ion in the
reaction :
3Br2 (aq) + 3H2O(g)
BrO3 (aq) + 5Br (aq) + 6H+
Varies as the concentration of reactants are changed.
Initial concentration
Exp. No.
[BrO ]
[Br ]
[H ]
1.
0.10
0.10
0.10
1.2 10
2.
0.20
0.10
0.10
2.4 10
3.
0.10
0.30
0.10
3.6 10
4.
0.20
0.10
0.15
5.4 10
Initial rate (mol L s )
3
3
3
3
Find (a) rate law (b) rate constant (c) rate when each of BrO3 , Br and H+ is 0.2 M.
Sol. (a)
Rate law can be derived as
Rate k[BrO3 ] [Br ] [H ]2

Hence, overall order of the reaction is 4.
(b)
Rate
[BrO3 ]
[Br ] [H ]
1.2 10 3
(0.1)4
= 12 L3 mol3 s1
(c)
Rate = 12(0.2)4
= 19.2 103 mol L1 s1
SECTION - B
Model Test Paper
Very Short Answer Type Questions :
1.
Express the rate of the following reaction in terms of disappearance of hydrogen in the reaction.
N2 (g) 3H2 (g) 2NH3 (g)
Sol.
2.
1 d[H2 ]
3 dt
In some cases, it is found that a large number of colloiding molecules have energy more than threshold value,
yet the reaction is slow. Why?
Sol. In such cases, the molecules do not collide in proper orientation.

3.
49
X2 , the rate of reaction becomes three times when the concentration of X is

For the reaction, 2X
increased 27 times. What is the order of reaction?
Sol. Order of the reaction =

4.
1
3
2NH3 (g), how is the rate of reaction expressions

For the reaction, 3H2 (g) + N2 (g)
d[H2 ]
and
dt
d[NH3 ]
interrelated?
dt
Sol.
5.
1 d[H2 ]
1 d[NH3 ]
3 dt
2 dt
For the reaction,
B
A + H2O
Rate [A]
What is its (i) molecularity (ii) order of the reaction?
Sol. Molecularity = 2, order of reaction = 1
6.
For the homogeneous decomposition of N2O5 into NO2 and O2
4NO2 (g) + O2 (g)

2N2O5 (g)
Rate =
1 [N2O5 ]
= k[N2O5 ]
2
t
Find out the order of reaction with respect to N2O5.

Sol. First order with respect to N2O5.
7.
What is the difference between average rate and instantaneous rate of a chemical reaction?
Sol. When change in concentration is measured over long period of time, we get average rate of reaction.
When change in concentration is measured over a very small period of time, or at a particular instant, it is
instantaneous rate.
8.
What is meant by rate constant k of a reaction? If the concentration is expressed in mol L1 units and time
in seconds, what would be the units for k
(i)
For a zero order reaction and
(ii)
For a first order reaction?
Sol. Rate constant is the rate of reaction when the concentration of reactants are unity.
Unit of k for zero order reaction : mol L1 s1
Unit of k for first order reaction : s1
9.
For the reaction at 500 K
CO2 (g) + NO(g)

NO2 (g) + CO(g)
The proposed mechanism is as follows :
(i)
NO + NO3 (Slow)
NO2 + NO2
(ii)
CO2 + NO2 (Fast)

NO3 + CO
What is the rate law for the reaction?

50
Sol. Rate law :
dx
= k[NO2 ]2
dt
It is because slowest step determines the rate law.

10. A first order decomposition reaction takes 40 minutes for 30% decomposition. Calculate t1/2 value.
Sol. 30% decomposition means (a x) = (a 0.3) = 0.7 a
k
2.303
a
log
t
ax
2.303
a
2.303
log
log 1.4286
40
0.7 a = 40
2.303
0.1551 = 0.00893 min1
40
t1/2 =
0.693
0.693
=
= 77.6 minutes
0.00893
k
11. For the reaction,

2N2O5 (g)
4NO2 (g) + O2 (g) .
If the concentration of NO2 increases by 3.0 103 mol/L in six seconds then what is the rate of reaction?
Sol. Rate of reaction =
1 [NO 2 ]
4
t
1 3 10 3
4
6
= 1.25 104 mol L1 s1

12. The following reaction was carried out in water.
2Cl + I2
Cl2 + 2I
The initial concentration of I was 0.5 mol/L and concentrations after 10 minutes was 0.46 mol/L. Calculate
the rate of disappearance of I and rate of appearance of iodine.
Sol. [I] = 0.46 0.50 = 0.04 mol L1
t = 10.0 0.0 = 10 min
Rate of disappearance of I =
[I ]
t
( 0.04)
10
= 0.004 mol/L/min
Rate of appearance of I2 =
=
1
(Rate of disappearance of I )
2
1
0.004
2
= 0.002 mol/L/min
51
13. The rate of formation of a dimer in a second order dimerisation reaction is 9.5 105 mol L1 s1 at 0.01
mol/L monomer concentration. Calculate the rate constant.
A2
Sol. 2A
Since, it is a second order reaction.
Rate = k[A]2
9.5 105 = k[0.01]2
k=
9.5 10 5
10 4
= 0.95 L mol1 s1
14. The half life period of a reaction of first order is 100 s. Calculate its rate constant.
Sol. For a first order reaction,
t1/2 =
0.693
k
k=
0.693
t1/2
k=
0.693
100
= 6.93 103 s1
15. Why the rate of a chemical reaction does not remain uniform throughout the reaction? Is it possible to have
reactions with a uniform rate?
Sol. It is because rate of reaction depends on concentration which changes with passage of time.
A reaction of zero order proceeds at a uniform rate.
16. The rate constant of a zero order reaction is 1 103 mol L1 s1. Starting with 50 moles, calculate the time
in minutes in which the concentration decreases to 10 moles.
Sol. For a zero order reaction, A0 At = kt
t=
A0 A t
k
50 10
10 3
= 40 103 s
t=
40 10 3
60
= 667 min
52
17. Rate constant k of a reaction varies with temperature, according to the equation :
logk = constant
Ea 1

2.303R T
When a graph is plotted for log k vs
Where Ea is the energy of activation for the reaction.
1
, a straight line with a slope 6670 K is obtained. Calculate energy
T
of activation for this reaction.

Sol. Slope = 6670 K
R = 8.314 J K1 mol1
Ea
Slope = 2.303R
Ea = Slope 2.303 R
= ( 6670) 2.303 8.314
= 127711.44 J/mol
= 127.71144 kJ/mol
18. Prove that the time required for the completion of
the completion of half of the reaction.
Sol. t 3/4 =
t3/4 =
3
th of reaction of first order is twice the time required for
4
[A 0 ]
2.303
log
1
k
[A ]
4 0
2.303
log 4
k
2.303 0.6021
k
1.386
k
2 0.693
k
= 2t1/2
19. The rate of a first order reaction is 0.04 mol L1 s1 at 10 minute and 0.03 mol L1 s1 at 20 minute after
initiation. Find half life of the reaction.
Sol. Rate = k[A]
0.04 = k[A]10 and 0.03 = k[A]20
[A]10 0.04 4
[A]20 0.03 3
Also, t
[A]
2.303
log 10
k
[A]20
10
k=
53
2.303
4
log
k
3
2.303
4
log
10
3
= 0.0288 min1
t1/2 =
0.693
0.693
=
k
0.0288
= 24.06 min
Long Answer Type Questions :

20. The experimental data for the reaction : 2A + B2
2AB is
Experiment
[A]
[B2]
Initial rate
0.50
0.50
1.6 10
0.50
1.00
3.2 10
1.00
1.00
3.2 10
4
4
4
Write the rate law equation.

Sol. Let the rate law be, r = k[A]x [B2]y
r1 = 1.6 104
= k[0.50]x [0.50]y
...(i)
r2 = 3.2 104
= k[0.50]x [1.00]y
...(ii)
r3 = 3.2 104
= k[1.00]x [1.00]y
...(iii)
Divide (ii) by (i)
r2
k (0.50)x (1.00)y
=
r1
k (0.50)x (0.50)y
3.2 10 4
1.6 10 4
y
1.00
2
0.50
2y = 2
y=1
54
Now divide (iii) by (ii)

r3
k (1.00)x (1.00)y
=
r2
k (0.50)x (0.50)y
3.2 10 4
3.2 10 4
(1.00)x
(0.50)x
=1
2x = 1
2x = 20
x=0
Rate law is r = k[A]0 [B2]1
21. The rate constant for an isomerisation reaction A B is 4.5 103 min1. If the initial concentration of A is
1 M, calculate the rate of reaction after 1 hour.
Sol. A B
k = 4.5 103 min1
[A]0 = 1 M
For 1st order reaction,
2.303
a
log10
t
ax
2.303
1
log10
60
ax
4.5 10 3
(a x) = 0.7634
Thus rate after 60 minute

= k (a x)
= 4.5 103 0.7634
= 3.4354 103 mol L1 s1.

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Chapter

Chemical Kinetics and Nuclear Chemistry

Z has zero order. What is the rate equation?

What is the rate-determining step of a reaction?

Sol. The slowest step is the rate determining step.

Radioactive disintegration is which type of reaction?

Define specific reaction rate.

Sol. Energy is required to cross the energy barrier.

Sol. Because rate of reaction is affected by change in concentration not amount.

Which is greater in magnitude threshold energy or activation energy?

Sol. Threshold energy.

Chemical Kinetics and Nuclear Chemistry

Solution of Assignment (Set-1)

Short Answer Type Questions :

be integral. For the given reaction, order of reaction =

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k [H2 ][Br2 ]3/2

What is the order of reaction? Write down unit of rate constant.

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Solution of Assignment (Set-1)

Chemical Kinetics and Nuclear Chemistry

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If volume of vessel is reduced to

Chemical Kinetics and Nuclear Chemistry

Solution of Assignment (Set-1)

Which reaction has the higher activation energy?

2.303 8.31 300 310

Solution of Assignment (Set-1)

Chemical Kinetics and Nuclear Chemistry

The use of a catalyst and

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Chemical Kinetics and Nuclear Chemistry

Solution of Assignment (Set-1)

29. Differentiate between reaction rate and reaction rate constant.

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Its unit depends on order of reaction.

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Give the differential rate law for above reaction.

Identify the reaction order, if the unit of rate constant is s1.

Rate law for above reaction is given by

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Order or reaction is one.

Solution of Assignment (Set-1)

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Chemical Kinetics and Nuclear Chemistry

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What is the rate and order of a reaction if the mechanism is

How does rate constant is related to concentration of the reactants?